JPH0675376A - Heat resistant negative photo-resist composition, photosensitive base material and negative pattern forming method - Google Patents
Heat resistant negative photo-resist composition, photosensitive base material and negative pattern forming methodInfo
- Publication number
- JPH0675376A JPH0675376A JP4287384A JP28738492A JPH0675376A JP H0675376 A JPH0675376 A JP H0675376A JP 4287384 A JP4287384 A JP 4287384A JP 28738492 A JP28738492 A JP 28738492A JP H0675376 A JPH0675376 A JP H0675376A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- heat
- photoresist composition
- negative photoresist
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1025—Preparatory processes from tetracarboxylic acids or derivatives and diamines polymerised by radiations
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は耐熱性ネガ型フォトレジ
スト組成物および感光性基材、ならびにネガ型パターン
形成方法に関するものである。FIELD OF THE INVENTION The present invention relates to a heat-resistant negative photoresist composition, a photosensitive substrate, and a negative pattern forming method.
【０００２】[0002]
【従来の技術】従来から耐熱性を有するものとして一般
に実用化されている感光性ポリイミドもしくはその前駆
体は、活性光線を照射することによって該ポリイミドも
しくは前駆体の現像液に対する溶解性を減少させ、各種
基板上に目的とするレリーフ像を形成するというネガ型
のものが主流となっている。2. Description of the Related Art A photosensitive polyimide or a precursor thereof which has been generally put into practical use as a material having heat resistance has been known to reduce the solubility of the polyimide or precursor in a developing solution by irradiating it with an actinic ray. Negative type that forms a desired relief image on various substrates is predominant.
【０００３】このような基板上に活性光線の照射部分が
残存するネガ型の感光性ポリイミドまたはその前駆体を
用いた耐熱性フォトレジストやその用途は多く提案され
ており、例えばポリイミド前駆体にエステル結合また
はイオン結合を介してメタクリロイル基を導入する方法
（特開昭４９−１１５４１号公報、特開昭５０−４０９
２２号公報、特開昭５４−１４５７９４号公報、特開昭
５６−３８０３８号公報など）、光重合性オレフィン
を有する可溶性ポリイミド（特開昭５９−１０８０３１
号公報、特開昭５９−２２０７３０号公報、特開昭５９
−２３２１２２号公報、特開昭６０−６７２９号公報、
特開昭６０−７２９２５号公報、特開昭６１−５７６２
０号公報など）、ベンゾフェノン骨格を有し、かつ窒
素原子が結合する芳香環のオルソ位にアルキル基を有す
る自己増感型ポリイミド（特開昭５９−２１９３３０号
公報、特開昭５９−２３１５３３号公報など）などが提
案されている。Many heat-resistant photoresists and their applications have been proposed which use a negative photosensitive polyimide or a precursor thereof in which an actinic ray irradiation portion remains on such a substrate. For example, an ester is used as a polyimide precursor. Method of introducing a methacryloyl group through a bond or an ionic bond (JP-A-49-11541 and JP-A-50-409).
No. 22, JP-A No. 54-145794, JP-A No. 56-38038, etc.), soluble polyimides having a photopolymerizable olefin (JP-A No. 59-108031).
JP, JP-A-59-220730, JP-A-59
No. 232122, Japanese Patent Laid-Open No. 60-6729,
JP-A-60-72925, JP-A-61-5762
No. 0), and a self-sensitized polyimide having a benzophenone skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (JP-A-59-219330, JP-A-59-231533). Gazettes) are proposed.
【０００４】しかしながら、上記従来のネガ型フォトレ
ジストではその機能上、解像度に問題があったり用途に
よっては製造時の歩留まり低下を招くなどの問題もあ
る。例えば、上記のものではエステル結合型の合成が
難しく、イオン結合型ではイミド化の際の熱硬化時に収
縮が起きたり、また、現像時にも膜減りが起きて現像、
熱硬化後の残存膜厚は初期のものの５０％程度になり、
寸法安定性に問題を有するものである。さらに、上記
およびのものでは用いるポリマーの骨格構造が限定さ
れるために、最終的に得られる皮膜の物性が限定されて
しまい、多種多用な要求特性に対して柔軟に対応でき
ず、多目的用途には不向きなものである。However, the above-mentioned conventional negative type photoresist has a problem in resolution due to its function and may cause a decrease in yield at the time of manufacture depending on its use. For example, in the above, it is difficult to synthesize an ester bond type, and in the ionic bond type, shrinkage may occur during heat curing during imidization, and film reduction may occur during development.
The residual film thickness after thermosetting is about 50% of the initial thickness,
It has a problem in dimensional stability. Furthermore, in the above and those described above, since the skeletal structure of the polymer used is limited, the physical properties of the film finally obtained are limited, and it is not possible to flexibly respond to a variety of versatile required properties, making it versatile. Is unsuitable.
【０００５】一方、ポリイミド前駆体にＮ−メチロール
アクリルアミドを配合してなる感光材についても報告さ
れている（Polymer Preprint Japan,39(8),2397(1990))
が、上記と同様、残存膜厚が５０％であり、寸法安定性
の点で問題を有する他、プリベークに長時間を要するな
どの問題点を有するものである。On the other hand, a photosensitive material prepared by blending N-methylolacrylamide with a polyimide precursor has also been reported (Polymer Preprint Japan, 39 (8), 2397 (1990)).
However, similarly to the above, the residual film thickness is 50%, which causes a problem in dimensional stability and also has a problem in that prebaking requires a long time.
【０００６】[0006]
【発明が解決しようとする課題】本発明は従来からのネ
ガ型フォトレジストが有する課題を解決し、レジスト形
成物質としての耐熱性を付与する樹脂であるポリイミド
前駆体の構造が比較的限定されず、しかも感度や解像度
も良好であり、かつ実用的な製造プロセスに適応できる
耐熱性ネガ型フォトレジスト組成物を提供することを目
的とする。The present invention solves the problems of conventional negative photoresists, and the structure of the polyimide precursor, which is a resin that imparts heat resistance as a resist-forming substance, is relatively unrestricted. Moreover, it is an object of the present invention to provide a heat-resistant negative photoresist composition which has good sensitivity and resolution and can be applied to a practical manufacturing process.
【０００７】また、他の目的は上記耐熱性ネガ型フォト
レジスト組成物を用いてなる感光性基材ならびにネガ型
パターン形成方法を提供することにある。Another object of the present invention is to provide a photosensitive substrate using the above heat-resistant negative photoresist composition and a negative pattern forming method.
【０００８】[0008]
【課題を解決するための手段】本発明者らは上記ネガ型
フォトレジスト組成物について、さらに検討を重ねた結
果、活性光線を照射することで塩基性を呈する特定の化
合物をポリイミド前駆体からなる樹脂成分に配合するこ
とによって、上記目的を達成できるネガ型フォトレジス
ト組成物が得られることを見い出し、本発明を完成する
に至った。As a result of further studies on the above negative type photoresist composition, the present inventors have found that a specific compound which exhibits basicity upon irradiation with actinic rays is composed of a polyimide precursor. It was found that a negative photoresist composition capable of achieving the above object can be obtained by blending the resin component with a resin component, and the present invention has been completed.
【０００９】即ち、本発明は下記式（化４）にて示され
る構造単位を有する樹脂成分と、That is, the present invention comprises a resin component having a structural unit represented by the following formula (Formula 4),
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】（但し、式中の矢印の結合は異性化によっ
て置換可能な結合を示し、Ｒ1 およびＲ2 はそれぞれ４
価および２価の芳香族または脂肪族炭化水素残基であ
る。） 下記式（化５）にて示される活性光線の照射にて塩基性
を呈する化合物と、(However, the bond of the arrow in the formula represents a bond which can be replaced by isomerization, and R 1 and R 2 are each 4
Valent and divalent aromatic or aliphatic hydrocarbon residues. ) A compound that exhibits basicity upon irradiation with an actinic ray represented by the following formula (Formula 5),
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】（但し、式中、Ｒ3 およびＲ4 は水素原子
もしくは炭素数１〜３のアルキル基、Ｒ5 およびＲ6 は
炭素数１〜４のアルキル基もしくはアルコキシル基、ア
ニリノ基、トルイジノ基、ベンジルオキシ基、アミノ
基、ジアルキルアミノ基から選ばれる一種であり、Ｘ1
〜Ｘ4 はそれぞれ水素原子、フッ素原子、ニトロ基、メ
トキシ基、ジアルキルアミノ基、アミノ基、シアノ基、
フッ素化アルキル基から選ばれる一種である。）を含有
してなる耐熱性ネガ型フォトレジスト組成物を提供する
ものである。(Wherein R 3 and R 4 are hydrogen atoms or an alkyl group having 1 to 3 carbon atoms, R 5 and R 6 are alkyl groups or alkoxy groups having 1 to 4 carbon atoms, anilino group, and toluidino group. , A benzyloxy group, an amino group, a dialkylamino group, X 1
To X 4 are each a hydrogen atom, a fluorine atom, a nitro group, a methoxy group, a dialkylamino group, an amino group, a cyano group,
It is a kind selected from fluorinated alkyl groups. The present invention provides a heat-resistant negative photoresist composition containing:
【００１４】また、本発明は上記耐熱性ネガ型フォトレ
ジスト組成物に、さらに下記式（化６）にて示される溶
解促進剤を含有させてなる耐熱性ネガ型フォトレジスト
組成物を提供するものである。The present invention also provides a heat-resistant negative photoresist composition comprising the above heat-resistant negative photoresist composition further containing a dissolution accelerator represented by the following formula (Formula 6). Is.
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】（但し、式中、Ｒ7 およびＲ8 は水素原子
もしくは炭素数１〜３のアルキル基、Ｒ9 およびＲ10は
水素原子、シアノ基、アセチル基、アミド基、ＣＯＯＲ
11基（Ｒ11は炭素数１〜５のアルキル基もしくはアルコ
キシル基、アニリノ基、トルイジノ基、ベンジルオキシ
基から選ばれる一種である。）から選ばれる一種であ
り、Ｘ5 は水素原子、フッ素原子、炭素数１〜３のアル
キル基、フッ素化アルキル基、フェニル基から選ばれる
一種である。） さらに、本発明は支持体の表面に上記耐熱性ネガ型フォ
トレジスト組成物を塗設してなる感光性基材を提供する
ものである。(Wherein, R 7 and R 8 are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, R 9 and R 10 are hydrogen atoms, cyano groups, acetyl groups, amido groups, COOR
11 groups (R 11 is a group selected from an alkyl group or an alkoxyl group having 1 to 5 carbon atoms, anilino group, toluidino group, and benzyloxy group), and X 5 is a hydrogen atom or a fluorine atom. , An alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group, and a phenyl group. Further, the present invention provides a photosensitive base material obtained by coating the heat-resistant negative photoresist composition on the surface of a support.
【００１７】また、本発明は上記耐熱性ネガ型フォトレ
ジスト組成物から得られたフィルムに、フォトマスクを
介して活性光線の照射を行い、さらに加熱処理を行なっ
たのち、塩基性現像液にて未露光部分を除去することを
特徴とするネガ型パターン形成方法を提供するものであ
る。Further, according to the present invention, the film obtained from the above heat-resistant negative photoresist composition is irradiated with an actinic ray through a photomask, further heat-treated, and then, with a basic developing solution. The present invention provides a negative pattern forming method characterized by removing an unexposed portion.
【００１８】本発明の耐熱性ネガ型フォトレジスト組成
物に用いられる樹脂成分は、レジスト形成の骨格物質と
して作用するものであって、上記（化４）に示す構造単
位を有するポリイミド前駆体である。上記（化４）で示
される構造単位中のＲ1 は、具体的にはベンゼン、ナフ
タレン、ペリレン、ジフェニル、ジフェニルエーテル、
ジフェニルスルホン、ジフェニルプロパン、ジフェニル
ヘキサフルオロプロパン、ベンゾフェノン、ブタン、シ
クロブタンなどの骨格を有する４価の芳香族または脂肪
族炭化水素残基が典型的な例として例示されるが、これ
らに限定されるものではない。好ましい基としてはベン
ゼン、ジフェニルおよびベンゾフェノンである。なお、
必要に応じてＲ1 として上記にて例示した基の二種類以
上を含有させることもできる。The resin component used in the heat-resistant negative photoresist composition of the present invention acts as a skeleton substance for resist formation, and is a polyimide precursor having the structural unit shown in (Chemical Formula 4) above. . R 1 in the structural unit represented by the above (chemical formula 4) is specifically benzene, naphthalene, perylene, diphenyl, diphenyl ether,
Typical examples include, but are not limited to, tetravalent aromatic or aliphatic hydrocarbon residues having a skeleton such as diphenyl sulfone, diphenyl propane, diphenyl hexafluoropropane, benzophenone, butane, and cyclobutane. is not. Preferred groups are benzene, diphenyl and benzophenone. In addition,
If necessary, R 1 may contain two or more kinds of the groups exemplified above.
【００１９】また、Ｒ2 としては、具体的にはジフェニ
ルエーテル、ジフェニルチオエーテル、ベンゾフェノ
ン、ジフェニルメタン、ジフェニルプロパン、ジフェニ
ルヘキサフルオロプロパン、ジフェニルスルホキシド、
ジフェニルスルホン、ビフェニル、ピリジン、ベンゼン
などの骨格を有する２価の芳香族または脂肪族炭化水素
残基が典型的な例として例示されるが、これらに限定さ
れるものではない。好ましい基としてはジフェニルエー
テル、ジフェニルスルホン、およびベンゼンである。な
お、必要に応じてＲ2 として上記にて例示した基の二種
類以上を含有させることもできる。Further, as R 2 , specifically, diphenyl ether, diphenyl thioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl sulfoxide,
A divalent aromatic or aliphatic hydrocarbon residue having a skeleton such as diphenyl sulfone, biphenyl, pyridine or benzene is exemplified as a typical example, but is not limited thereto. Preferred groups are diphenyl ether, diphenyl sulfone, and benzene. If necessary, R 2 may contain two or more types of the groups exemplified above.
【００２０】このような構造単位を有する樹脂成分は、
例えば上記Ｒ1 を分子内に有する芳香族もしくは脂肪族
テトラカルボン酸二無水物と、上記Ｒ2 を分子内に有す
る芳香族もしくは脂肪族ジアミンの略等モル量を、Ｎ−
メチル−２−ピロリドン、ジメチルアセトアミド、ジメ
チルホルムアミド、ジメチルスルホキシド、ヘキサメチ
ルホスホルアミドなどの有機溶媒中にて反応させること
によって得ることができる。The resin component having such a structural unit is
For example, an approximately equimolar amount of the aromatic or aliphatic tetracarboxylic acid dianhydride having R 1 in the molecule and the aromatic or aliphatic diamine having R 2 in the molecule is N-
It can be obtained by reacting in an organic solvent such as methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide.
【００２１】本発明の耐熱性ネガ型フォトレジスト組成
物の第１は、上記（化４）にて示される構造単位を有す
る樹脂成分に、上記（化５）で示される感光性を有する
化合物を含有させてなることを特徴とする。つまり、該
組成物には上記（化５）にて示される活性光線の照射に
よって塩基性を呈する感光性の化合物が配合されてお
り、必要に応じて公知の増感剤とが組み合わされて配合
される。上記感光性を有する化合物（化５）は、（化
４）にて示される樹脂成分１００重量部に対して５〜５
０重量部、好ましくは１０〜４０重量部の範囲で配合す
ることが望ましい。配合量が少ない場合は露光部の溶解
阻止能が悪くなって溶解性コントラストが不鮮明になり
やすい。また、配合量が多い場合は溶液状態で保存する
際に固形分の析出が生じ、溶液保存性やパターン形成性
に悪影響を与え、さらに、ネガ型パターン形成後に熱処
理を施すと膜減りが大きくなって機械的強度も低下させ
ることがある。The first of the heat-resistant negative photoresist compositions of the present invention is to add a photosensitive compound represented by the above (Chemical formula 5) to a resin component having the structural unit represented by the above (Chemical formula 4). It is characterized in that it is contained. That is, the composition is blended with a photosensitive compound represented by the above (Chemical Formula 5) which exhibits basicity upon irradiation with actinic rays, and is blended with a known sensitizer in combination if necessary. To be done. The compound (Chemical Formula 5) having photosensitivity is 5 to 5 with respect to 100 parts by weight of the resin component represented by (Chemical Formula 4).
It is desirable to blend in an amount of 0 parts by weight, preferably 10 to 40 parts by weight. When the compounding amount is too small, the dissolution inhibiting ability of the exposed area becomes poor and the solubility contrast tends to become unclear. In addition, when the blending amount is large, solid content is precipitated during storage in a solution state, which adversely affects solution storability and pattern formability. Further, when heat treatment is performed after forming a negative pattern, film loss becomes large. Mechanical strength may also be reduced.
【００２２】本発明において前記化合物（化５）は、活
性光線に曝されると、分子構造が分子内転移を経てピリ
ジン骨格を有する構造に変化して塩基性を呈するように
なり、その後の熱処理によってさらに化学反応が進行し
て、その結果、前記（化４）にて示される構造単位を有
する樹脂成分との間で、もしくは単独で何らかの相互作
用が生じてアルカリ溶解性が低下し、良好なネガ型パタ
ーン形成ができるものと推測される。In the present invention, the compound (Chemical Formula 5), when exposed to actinic rays, changes its molecular structure to a structure having a pyridine skeleton through intramolecular transition and becomes basic, and the subsequent heat treatment. The chemical reaction further progresses, and as a result, some interaction occurs with the resin component having the structural unit represented by the above (Chemical Formula 4) or by itself, and the alkali solubility decreases, resulting in a favorable reaction. It is presumed that a negative pattern can be formed.
【００２３】このような（化５）として好適な化合物と
しては、例えば２，６−ジメチル−３，５−ジシアノ−
４−（２’−ニトロフェニル）−１，４−ジヒドロピリ
ジン、２，６−ジメチル−３，５−ジアセチル−４−
（２’−ニトロフェニル）−１，４−ジヒドロピリジ
ン、２，６−ジメチル−３，５−ジアセチル−４−
（２’，４’−ジニトロフェニル）−１，４−ジヒドロ
ピリジンなどが挙げられる。A compound suitable as such (Chemical Formula 5) is, for example, 2,6-dimethyl-3,5-dicyano-
4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-
(2'-Nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4-
(2 ', 4'-dinitrophenyl) -1,4-dihydropyridine and the like.
【００２４】（化５）にて示される化合物は、例えば置
換ベンズアルデヒドと２倍モル量のアミノクロトニトリ
ルとを氷酢酸中で、還流させながら反応させたり、置換
ベンズアルデヒドと２倍モル量のアセチルアセトンと等
モル量のアンモニアとをメタノール中で反応させたり、
例えば一般的な１，４−ジヒドロピリジン誘導体の合成
法（例えば、J.Chem.Soc.,1931,1835,1931) に従って得
ることができる。The compound represented by the formula (5) is, for example, a reaction of substituted benzaldehyde with 2-fold molar amount of aminocrotonitrile in refluxing glacial acetic acid, or with substituted benzaldehyde and 2-fold molar amount of acetylacetone. Reacting with equimolar amount of ammonia in methanol,
For example, it can be obtained according to a general method for synthesizing a 1,4-dihydropyridine derivative (for example, J. Chem. Soc., 1931 , 1835, 1931 ).
【００２５】また、本発明の耐熱性ネガ型フォトレジス
ト組成物の第２は、上記（化４）にて示される構造単位
を有する樹脂成分に、上記（化５）で示される感光性を
有する化合物を含有させてなる組成物に、さらに上記
（化６）にて示される溶解促進剤を含有させてなること
を特徴とする。該組成物に含有させる（化６）にて示さ
れる溶解促進剤は活性光線の照射に対しては全く不活性
であるが、現像時において未露光部の溶解速度を促進す
る効果を有するので、現像速度を向上させて実用上有用
な組成物とすることができる。The second heat-resistant negative photoresist composition of the present invention has the photosensitivity shown in the above (Chemical formula 5) to the resin component having the structural unit shown in the above (Chemical formula 4). It is characterized in that the composition containing the compound further contains the dissolution accelerator represented by the above (formula 6). The dissolution accelerator represented by (Chemical Formula 6) contained in the composition is completely inactive to the irradiation of actinic rays, but has the effect of promoting the dissolution rate of the unexposed area during development, It is possible to improve the developing rate to obtain a practically useful composition.
【００２６】このような（化６）として好適な化合物と
しては、例えば２，６−ジメチル−３，５−ジシアノ−
４−メチル−１，４−ジヒドロピリジンや、２，６−ジ
メチル−３，５−ジシアノ−１，４−ジヒドロピリジン
などが挙げられる。A compound suitable as such (Chemical Formula 6) is, for example, 2,6-dimethyl-3,5-dicyano-
4-methyl-1,4-dihydropyridine, 2,6-dimethyl-3,5-dicyano-1,4-dihydropyridine and the like can be mentioned.
【００２７】上記溶解促進剤として含有させる化合物
（化６）は、（化４）にて示される樹脂成分１００重量
部に対して５〜５０重量部、好ましくは５〜１５重量部
の範囲で配合することが望ましい。配合量が少ない場合
は現像時に未露光部の樹脂成分の溶解速度を速めること
が期待できず、また、多く配合した場合は最終的な加熱
キュアーののちに膜減りが大きくなったり、露光部分の
溶解阻止能が低下したりする恐れがあるので好ましくな
い。The compound (Chemical Formula 6) to be contained as the above-mentioned dissolution accelerator is compounded in an amount of 5 to 50 parts by weight, preferably 5 to 15 parts by weight, relative to 100 parts by weight of the resin component shown in (Chemical Formula 4). It is desirable to do. If the blending amount is small, it cannot be expected to accelerate the dissolution rate of the resin component in the unexposed area at the time of development, and if the blending amount is large, the film loss becomes large after the final heating cure, or the exposed portion It is not preferable because the dissolution inhibiting ability may be lowered.
【００２８】次に、本発明の耐熱性ネガ型フォトレジス
ト組成物を用いて画像を形成する方法の一例を示す。Next, an example of a method for forming an image using the heat-resistant negative photoresist composition of the present invention will be shown.
【００２９】まず、前記（化４）にて示した樹脂成分
と、前記（化５）または（化５）と（化６）にて示す化
合物を、前記有機溶剤に溶解して感光液を調製する。次
いで、この感光液を基材上に乾燥後の膜厚が１〜３０μ
ｍ、好ましくは１０〜２０μｍとなるように塗布する。First, the resin component shown in (Chemical formula 4) and the compound shown in (Chemical formula 5) or (Chemical formula 5) and (Chemical formula 6) are dissolved in the organic solvent to prepare a photosensitive solution. To do. Then, the film thickness after drying this photosensitive solution on the substrate is 1 to 30 μm.
m, preferably 10 to 20 μm.
【００３０】塗布した塗膜を乾燥（８０℃、１０分程
度）した後に通常のフォトマスクを通して露光を行な
い、露光後、後加熱（１５０〜２００℃、好ましくは１
７０℃以上で１０分程度）を行ったのち、未照射部分を
除去すべく浸漬法やスプレー法などを用いて現像処理を
行う。現像処理に用いる現像液としては、露光膜の未照
射部を適当な時間内で完全に溶解除去できるものが好ま
しく、水酸化ナトリウム、水酸化カリウムなどの無機ア
ルカリ性水溶液、またはプロピルアミン、ブチルアミ
ン、モノエタノールアミン、テトラメチルアンモニウム
ハイドロオキサイド、コリンなどの有機アルカリ性水溶
液などを単独もしくは二種以上混合して用いる。また、
このアルカリ性水溶液には必要に応じてアルコール類な
どの有機溶剤や、各種界面活性剤を含有させることもで
きる。The applied coating film is dried (80 ° C., about 10 minutes) and then exposed through a normal photomask. After exposure, post-heating (150 to 200 ° C., preferably 1
After performing the treatment at 70 ° C. or higher for about 10 minutes), a developing process is performed using a dipping method, a spray method, or the like to remove the unirradiated portion. The developer used for the development treatment is preferably one that can completely dissolve and remove the unirradiated portion of the exposed film within a suitable time, and an inorganic alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, or propylamine, butylamine, mono An organic alkaline aqueous solution of ethanolamine, tetramethylammonium hydroxide, choline or the like is used alone or in combination of two or more. Also,
If necessary, the alkaline aqueous solution may contain organic solvents such as alcohols and various surfactants.
【００３１】現像したのち、リンス液で洗浄することに
より所望のネガ型パターンを有する樹脂画像が形成され
る。After the development, a rinse solution is washed to form a resin image having a desired negative pattern.
【００３２】以上のようにして得られた画像は、最終的
に高温加熱処理（約２００〜４５０℃）をすることによ
って、ポリイミド前駆体が脱水閉環してイミド化し、耐
熱性を有するポリイミド画像となるのである。The image thus obtained is finally subjected to a high-temperature heat treatment (about 200 to 450 ° C.) to dehydrate and ring the polyimide precursor to form an imidized polyimide image having heat resistance. It will be.
【００３３】[0033]
【実施例】以下に本発明の実施例を示し、本発明をさら
に具体的に説明する。EXAMPLES The present invention will be described in more detail below by showing Examples of the present invention.
【００３４】実施例１ ビフェニルテトラカルボン酸二無水物とパラフェニレン
ジアミンの略等モル量を、ジメチルアセトアミド中にて
モノマー濃度２０重量％で室温下、２４時間反応させて
（化４）にて示されるポリイミド前駆体溶液を得た。Example 1 Approximately equimolar amounts of biphenyltetracarboxylic dianhydride and para-phenylenediamine were reacted in dimethylacetamide at a monomer concentration of 20% by weight at room temperature for 24 hours, and the reaction was shown in Chemical formula 4. To obtain a polyimide precursor solution.
【００３５】上記にて得たポリイミド前駆体溶液の固形
分１００重量部に対して、（化５）中、Ｒ3 およびＲ4
がメチル基で、Ｘ1 、Ｘ2 、Ｘ3 およびＸ4 が水素原子
である化合物（以下、ｏ−ＮＣＮという）を３０重量部
を添加し、均一に溶解した。With respect to 100 parts by weight of the solid content of the polyimide precursor solution obtained above, R 3 and R 4 in (Chemical Formula 5)
Is a methyl group and X 1 , X 2 , X 3 and X 4 are hydrogen atoms (hereinafter referred to as o-NCN) in an amount of 30 parts by weight and uniformly dissolved.
【００３６】この溶液をシリコンウエハ上にスピンコー
ターを用いて回転数２２００ｒｐｍ／２０ｓｅｃでスピ
ンコートして、８０℃のホットプレート上で１０分間予
備乾燥を行い、乾燥膜厚約１８μｍの塗膜を形成した。
そののち、ガラスマスクを通して２５０Ｗ超高圧水銀灯
にガラスフィルターをかけた４３６ｎｍの波長の活性光
線を用い、光源から３０ｃｍのところで３分間、真空密
着露光を行った。This solution was spin-coated on a silicon wafer using a spin coater at a rotation speed of 2200 rpm / 20 sec and pre-dried on a hot plate at 80 ° C. for 10 minutes to form a coating film having a dry film thickness of about 18 μm. did.
After that, vacuum contact exposure was performed at a distance of 30 cm from the light source for 3 minutes using an actinic ray having a wavelength of 436 nm filtered through a glass filter through a glass mask with a 250 W ultrahigh pressure mercury lamp.
【００３７】露光後、１８５℃で１０分間加熱したの
ち、テトラメチルアンモニウムハイドロオキサイド３重
量％水溶液／メチルアルコール（体積比２／１）からな
る現像液で４分間現像、水でリンスしたところ、光照射
部のみが鮮明に基板上に残存するネガ型パターンを得
た。After the exposure, it was heated at 185 ° C. for 10 minutes, then developed for 4 minutes with a developer consisting of a 3% by weight aqueous solution of tetramethylammonium hydroxide / methyl alcohol (volume ratio 2/1) and rinsed with water. A negative pattern was obtained in which only the irradiated part remained clearly on the substrate.
【００３８】このパターンは高温加熱（４００℃／２時
間）してイミド化した場合、残存膜厚率は約７５％であ
った。なお、最終的に得られたポリイミドフィルムは茶
色状であって、実用レベルの諸特性を充分に備えるもの
であった。When this pattern was heated at a high temperature (400 ° C./2 hours) and imidized, the residual film thickness ratio was about 75%. The finally obtained polyimide film had a brown color and was sufficiently provided with various properties at a practical level.
【００３９】実施例２ 実施例１においてポリイミド前駆体を調製する際の有機
溶媒を、ジメチルアセトアミドからＮ−メチル−２−ピ
ロリドンに変えた以外は、実施例１と同様にしてネガ型
パターンを形成した。Example 2 A negative type pattern was formed in the same manner as in Example 1 except that dimethylacetamide was replaced with N-methyl-2-pyrrolidone as the organic solvent in the preparation of the polyimide precursor. did.
【００４０】このとき予備乾燥に１００℃を必要とした
が、その他は実施例１と同様、良好なパターンが得られ
た。At this time, 100 ° C. was required for preliminary drying, but other than that, a good pattern was obtained as in Example 1.
【００４１】実施例３ 実施例１においてｏ−ＮＣＮの代わりに、（化５）中、
Ｒ3 およびＲ4 がメチル基で、Ｘ1 、Ｘ3 およびＸ4 が
水素原子で、Ｘ2 がニトロ基である化合物（以下、２，
４−ＮＣＮという）を同量用いた以外は、実施例１と同
様にしてネガ型パターンを形成した結果、実施例１と同
様、良好なパターンが得られた。Example 3 Instead of o-NCN in Example 1, in (Chemical Formula 5),
A compound in which R 3 and R 4 are methyl groups, X 1 , X 3 and X 4 are hydrogen atoms, and X 2 is a nitro group (hereinafter, referred to as 2,
As a result of forming a negative pattern in the same manner as in Example 1 except that the same amount of (4-NCN) was used, a good pattern was obtained as in Example 1.
【００４２】比較例１ 実施例１においてｏ−ＮＣＮの代わりに、（化５）中、
Ｒ3 およびＲ4 がメチル基で、Ｘ1 、Ｘ3 およびＸ4 が
水素原子で、Ｘ2 がニトロ基で、１，４−ジヒドロピリ
ジン環の３，５位のシアノ基の代わりに−ＣＯＯＣＨ3
基である化合物（以下、２，４−ＮＥという）を同量用
い、露光後の加熱を１６５℃で１０分とした以外は、実
施例１と同様にしてパターンを形成したが、得られたパ
ターンは未照射部が基板上に残存するポジ型パターンで
あった。 実施例４ 実施例１においてｏ−ＮＣＮの代わりに、（化６）中、
Ｒ3 、Ｒ4 、Ｒ5 およびＲ6 がメチル基で、Ｘ1 、
Ｘ2 、Ｘ3 およびＸ4 が水素原子である化合物（以下、
２，４−ＮＡという）を同量用いた以外は、実施例１と
同様にしてネガ型パターンを形成した結果、実施例１と
同様、良好なパターンが得られた。Comparative Example 1 Instead of o-NCN in Example 1, in (Chemical Formula 5),
R 3 and R 4 are methyl groups, X 1 , X 3 and X 4 are hydrogen atoms, X 2 is a nitro group, and —COOCH 3 instead of the cyano group at the 3,5-position of the 1,4-dihydropyridine ring.
A pattern was formed in the same manner as in Example 1 except that the same amount of the compound as the group (hereinafter, referred to as 2,4-NE) was used, and the heating after exposure was performed at 165 ° C. for 10 minutes. The pattern was a positive type pattern in which the unirradiated part remained on the substrate. Example 4 Instead of o-NCN in Example 1, in (Chemical Formula 6),
R 3 , R 4 , R 5 and R 6 are methyl groups, and X 1 ,
A compound in which X 2 , X 3 and X 4 are hydrogen atoms (hereinafter,
As a result of forming a negative pattern in the same manner as in Example 1 except that the same amount of (2,4-NA) was used, a good pattern was obtained as in Example 1.
【００４３】実施例５ 実施例４においてポリイミド前駆体を調製する際の有機
溶媒を、ジメチルアセトアミドからＮ−メチル−２−ピ
ロリドンに変えた以外は、実施例４と同様にしてネガ型
パターンを形成した。Example 5 A negative pattern was formed in the same manner as in Example 4 except that dimethylacetamide was replaced by N-methyl-2-pyrrolidone as the organic solvent in the preparation of the polyimide precursor. did.
【００４４】このとき予備乾燥に１００℃を必要とした
が、その他は実施例４と同様、良好なパターンが得られ
た。At this time, although 100 ° C. was required for the preliminary drying, a good pattern was obtained in the same manner as in Example 4 except for the above.
【００４５】実施例６ 実施例４においてｏ−ＮＡの代わりに、（化６）中、Ｒ
3 、Ｒ4 、Ｒ5 およびＲ6 がメチル基で、Ｘ1 、Ｘ3 お
よびＸ4 が水素原子で、Ｘ2 がニトロ基である化合物
（以下、２，４−ＮＡという）を同量用いた以外は、実
施例４と同様にしてネガ型パターンを形成した結果、実
施例４と同様、良好なパターンが得られた。Example 6 Instead of o-NA in Example 4, R in
The same amount of a compound in which 3 , R 4 , R 5 and R 6 are methyl groups, X 1 , X 3 and X 4 are hydrogen atoms, and X 2 is a nitro group (hereinafter referred to as 2,4-NA) As a result of forming a negative pattern in the same manner as in Example 4 except that it was present, a good pattern was obtained as in Example 4.
【００４６】比較例２ 実施例４においてｏ−ＮＡの代わりに、比較例１にて用
いた２，４−ＮＥを同量用い、露光後の加熱を１６５℃
で１０分とした以外は、実施例４と同様にしてパターン
を形成したが、得られたパターンは未照射部が基板上に
残存するポジ型パターンであった。 実施例７ 実施例１にて得たポリイミド前駆体溶液の固形分１００
重量部に対して、（化５）中、Ｒ3 およびＲ4 がメチル
基で、Ｘ1 、Ｘ2 、Ｘ3 、Ｘ4 が水素原子、Ｒ 5 、Ｒ6
がメチル基である化合物（以下、ＤＡｃという）を２０
重量部、（化６）中、Ｘ5 がメチル基、Ｒ7 およびＲ8
がメチル基、Ｒ9 およびＲ10がシアノ基である化合物
（以下、ＣＨ3 −ＣＮという）を１０重量部添加して、
均一に溶解した。Comparative Example 2 Instead of o-NA in Example 4, used in Comparative Example 1.
The same amount of 2,4-NE was used, and heating after exposure was performed at 165 ° C.
The pattern was obtained in the same manner as in Example 4 except that 10 minutes was set.
Was formed, but the resulting pattern had unirradiated areas on the substrate.
It was a positive pattern that remained. Example 7 Solid content 100 of the polyimide precursor solution obtained in Example 1.
R in (Chemical Formula 5) relative to parts by weight3And RFourIs methyl
By X1, X2, X3, XFourIs a hydrogen atom, R Five, R6
A compound in which is a methyl group (hereinafter referred to as DAc) is 20
By weight, in (Chemical Formula 6), XFiveIs a methyl group, R7And R8
Is a methyl group, R9And RTenIs a cyano group
(Hereinafter, CH3-CN) is added by 10 parts by weight,
It dissolved uniformly.
【００４７】この溶液を用いた以外は実施例１と同様に
してネガ型パターンを形成した。このパターンは高温加
熱（４００℃／２時間）してイミド化した場合、残存膜
厚率は約７５％であり、また現像速度は実施例１の場合
と比べて速く、約１．５〜２倍程度であった。なお、最
終的に得られたポリイミドフィルムは茶色状であり、実
用レベルの諸特性を充分に備えるものであった。A negative pattern was formed in the same manner as in Example 1 except that this solution was used. When this pattern was imidized by heating at a high temperature (400 ° C./2 hours), the residual film thickness rate was about 75%, and the developing rate was higher than that of Example 1, and about 1.5-2. It was about double. The finally obtained polyimide film had a brown color and was sufficiently provided with various properties at a practical level.
【００４８】実施例８ 実施例７においてＤＡｃの代わりに、（化５）中のＲ3
およびＲ4 がメチル基で、Ｘ1 、Ｘ3 およびＸ4 が水素
原子、Ｘ2 がニトロ基で、Ｒ5 、Ｒ6 がメトキシ基であ
る化合物（以下、２，４−ＤＥｓという）を同量用いた
以外は、実施例１と同様にしてネガ型パターンを形成し
た結果、実施例７と同様、良好なパターンが得られた。Example 8 Instead of DAc in Example 7, R 3 in (Chemical Formula 5)
And R 4 is a methyl group, X 1 , X 3 and X 4 are hydrogen atoms, X 2 is a nitro group, and R 5 and R 6 are methoxy groups (hereinafter referred to as 2,4-DEs). As a result of forming a negative pattern in the same manner as in Example 1 except that the amount was used, a good pattern was obtained as in Example 7.
【００４９】実施例９ 実施例７においてＤＡｃの代わりに、（化５）中のＲ3
およびＲ4 がメチル基で、Ｘ1 、Ｘ3 およびＸ4 が水素
原子、Ｘ2 がニトロ基で、１，４−ジヒドロピリジン環
の３，５位がメチル基である化合物（以下、２，４−Ｄ
Ａｃという）を同量用い、露光後の加熱を２００℃で１
０分間とした以外は、実施例７と同様にしてネガ型パタ
ーンを形成した。Example 9 Instead of DAc in Example 7, R 3 in (Chemical Formula 5)
And R 4 is a methyl group, X 1 , X 3 and X 4 are hydrogen atoms, X 2 is a nitro group, and the 3,4-position of the 1,4-dihydropyridine ring is a methyl group (hereinafter, 2, 4 -D
The same amount of Ac) is used, and heating after exposure is performed at 200 ° C. for 1 hour.
A negative pattern was formed in the same manner as in Example 7 except that the time was 0 minutes.
【００５０】その結果、実施例７と同様に良好なパター
ンが得られた。As a result, a good pattern was obtained as in Example 7.
【００５１】実施例１０ 実施例７において露光後の加熱を１３０℃で１０分間行
い、さらに２００℃で１０分間行った以外は、実施例７
と同様にしてネガ型パターンを形成した。Example 10 Example 7 was repeated except that the heating after exposure was carried out at 130 ° C. for 10 minutes and then at 200 ° C. for 10 minutes.
A negative pattern was formed in the same manner as in.
【００５２】このパターンを３６０℃で２時間高温加熱
してイミド化して得られるポリイミドフィルムの物性
は、実施例７のものよりも機械的強度の点で優れたもの
であった。The polyimide film obtained by heating this pattern at 360 ° C. for 2 hours at a high temperature for imidization was superior to that of Example 7 in mechanical strength.
【００５３】実施例１１ 実施例７においてプリベークを９０℃で３０分間とした
以外は、実施例７と同様にしてネガ型のパターンを形成
した。このパターンを実施例１０と同様にして高温加熱
してイミド化してポリイミドフィルムとした結果、この
フィルムの物性は実施例７のものよりも機械的強度の点
で優れたものであった。Example 11 A negative pattern was formed in the same manner as in Example 7 except that prebaking was carried out at 90 ° C. for 30 minutes. As a result of heating this pattern at a high temperature in the same manner as in Example 10 to imidize it to obtain a polyimide film, the physical properties of this film were superior to those of Example 7 in terms of mechanical strength.
【００５４】[0054]
【発明の効果】本発明の耐熱性ネガ型フォトレジスト組
成物は、含有する特定の感光性化合物が主に光吸収する
波長の活性光線を照射することによって、照射部分のア
ルカリ溶解性が低下して照射部分と未照射部分でのアル
カリ性現像液に対する大きな溶解速度差が生じ、高感
度、高解像度の実用に耐えうるネガ型パターンの形成が
可能となる。また、特定の溶解促進剤を併存させること
によって、実用的な溶解時間でパターン形成を行うこと
ができるものである。INDUSTRIAL APPLICABILITY The heat-resistant negative photoresist composition of the present invention reduces the alkali solubility of the irradiated part by irradiating with an actinic ray having a wavelength which is mainly absorbed by the specific photosensitive compound contained therein. As a result, a large difference in dissolution rate with respect to the alkaline developing solution occurs between the irradiated portion and the non-irradiated portion, and it is possible to form a negative pattern having high sensitivity and high resolution that can be practically used. Further, by coexisting a specific dissolution accelerator, it is possible to form a pattern in a practical dissolution time.
【００５５】さらに、比較的簡単にしかも安価に所望の
パターン形成が行え、高品質の製品供給が可能となるも
のである。さらに、高温加熱処理して得られる最終物は
耐熱性や電気的特性、機械的特定に優れるので、半導体
工業における固体素子や、回路基板の保護膜、絶縁膜を
形成するための材料としても好適なものである。Furthermore, desired patterns can be formed relatively easily and inexpensively, and high quality products can be supplied. Furthermore, since the final product obtained by high-temperature heat treatment has excellent heat resistance, electrical characteristics, and mechanical specification, it is also suitable as a material for forming a solid element in the semiconductor industry, a protective film for a circuit board, and an insulating film. It is something.
Claims (5)
有する樹脂成分と、 【化１】 （但し、式中の矢印の結合は異性化によって置換可能な
結合を示し、Ｒ1 およびＲ2 はそれぞれ４価および２価
の芳香族または脂肪族炭化水素残基である。） 下記式（化２）にて示される活性光線の照射にて塩基性
を呈する化合物と、 【化２】 （但し、式中、Ｒ3 およびＲ4 は水素原子もしくは炭素
数１〜３のアルキル基、Ｒ5 およびＲ6 は炭素数１〜４
のアルキル基もしくはアルコキシル基、アニリノ基、ト
ルイジノ基、ベンジルオキシ基、アミノ基、ジアルキル
アミノ基から選ばれる一種であり、Ｘ1 〜Ｘ4 はそれぞ
れ水素原子、フッ素原子、ニトロ基、メトキシ基、ジア
ルキルアミノ基、アミノ基、シアノ基、フッ素化アルキ
ル基から選ばれる一種である。）を含有してなる耐熱性
ネガ型フォトレジスト組成物。1. A resin component having a structural unit represented by the following formula (Formula 1); (However, the arrow bond in the formula represents a bond which can be replaced by isomerization, and R 1 and R 2 are tetravalent and divalent aromatic or aliphatic hydrocarbon residues, respectively.) A compound which exhibits basicity upon irradiation with actinic rays, which is represented by 2), and (However, in the formula, R 3 and R 4 are hydrogen atoms or an alkyl group having 1 to 3 carbon atoms, and R 5 and R 6 are 1 to 4 carbon atoms.
Is an alkyl group or alkoxyl group, anilino group, toluidino group, benzyloxy group, amino group, dialkylamino group, X 1 to X 4 are each a hydrogen atom, a fluorine atom, a nitro group, a methoxy group, a dialkyl group. It is a kind selected from an amino group, an amino group, a cyano group, and a fluorinated alkyl group. ) A heat-resistant negative photoresist composition containing:
スト組成物に、さらに下記式（化３）にて示される溶解
促進剤を含有させてなる耐熱性ネガ型フォトレジスト組
成物。 【化３】 （但し、式中、Ｒ7 およびＲ8 は水素原子もしくは炭素
数１〜３のアルキル基、Ｒ9 およびＲ10は水素原子、シ
アノ基、アセチル基、アミド基、ＣＯＯＲ11基（Ｒ11は
炭素数１〜５のアルキル基もしくはアルコキシル基、ア
ニリノ基、トルイジノ基、ベンジルオキシ基から選ばれ
る一種である。）から選ばれる一種であり、Ｘ5 は水素
原子、フッ素原子、炭素数１〜３のアルキル基、フッ素
化アルキル基、フェニル基から選ばれる一種である。）2. A heat-resistant negative photoresist composition comprising the heat-resistant negative photoresist composition according to claim 1 further containing a dissolution accelerator represented by the following formula (Formula 3). [Chemical 3] (However, in the formula, R 7 and R 8 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 9 and R 10 are a hydrogen atom, a cyano group, an acetyl group, an amide group, and a COOR 11 group (R 11 is a carbon atom. 1 to 5 selected from an alkyl group or an alkoxyl group having 1 to 5 groups, anilino group, toludino group, and benzyloxy group), and X 5 represents a hydrogen atom, a fluorine atom, or a C 1 to C 3 group. It is one kind selected from alkyl group, fluorinated alkyl group and phenyl group.)
耐熱性ネガ型フォトレジスト組成物を塗設してなる感光
性基材。3. A photosensitive substrate obtained by coating the surface of a support with the heat-resistant negative photoresist composition according to claim 1.
ガ型フォトレジスト組成物から得られたフィルムに、フ
ォトマスクを介して活性光線の照射を行い、さらに加熱
処理を行なったのち、塩基性現像液にて未露光部分を除
去することを特徴とするネガ型パターン形成方法。4. A film obtained from the heat-resistant negative photoresist composition according to claim 1, is irradiated with an actinic ray through a photomask, and then heat-treated. A method for forming a negative pattern, which comprises removing an unexposed portion with a basic developing solution.
求項４記載のネガ型パターン形成方法。5. The negative pattern forming method according to claim 4, wherein the temperature of the heat treatment is 170 ° C. or higher.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04287384A JP3093055B2 (en) | 1992-07-07 | 1992-10-26 | Heat resistant negative photoresist composition, photosensitive substrate, and negative pattern forming method |
| DE1993608403 DE69308403T2 (en) | 1992-07-07 | 1993-07-05 | Heat resistant, negative working photoresist composition, photosensitive substrate and method of making a negative pattern |
| EP19930110730 EP0578177B1 (en) | 1992-07-07 | 1993-07-05 | Heat-resistant negative photoresist composition, photosensitive substrate, and process for forming negative pattern |
| US08/769,829 US5851736A (en) | 1991-03-05 | 1996-12-20 | Heat-resistant photoresist composition, photosensitive substrate, and process for forming heat-resistant positive or negative pattern |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-179685 | 1992-07-07 | ||
| JP17968592 | 1992-07-07 | ||
| JP04287384A JP3093055B2 (en) | 1992-07-07 | 1992-10-26 | Heat resistant negative photoresist composition, photosensitive substrate, and negative pattern forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0675376A true JPH0675376A (en) | 1994-03-18 |
| JP3093055B2 JP3093055B2 (en) | 2000-10-03 |
Family
ID=26499462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04287384A Expired - Lifetime JP3093055B2 (en) | 1991-03-05 | 1992-10-26 | Heat resistant negative photoresist composition, photosensitive substrate, and negative pattern forming method |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0578177B1 (en) |
| JP (1) | JP3093055B2 (en) |
| DE (1) | DE69308403T2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07271034A (en) * | 1994-03-29 | 1995-10-20 | Nitto Denko Corp | Heat-resistant negative photoresist composition, photosensitive substrate and negative pattern forming method |
| US5521034A (en) * | 1993-05-07 | 1996-05-28 | Nitto Denko Corporation | Individual identification label |
| WO1998004959A1 (en) * | 1996-07-29 | 1998-02-05 | Nitto Denko Corporation | Negative photoresist compositions and use thereof |
| US6746816B2 (en) | 2000-11-08 | 2004-06-08 | Nitto Denko Corporation | Photosensitive resin composition and circuit board |
| US7008752B2 (en) | 2004-03-17 | 2006-03-07 | Nitto Denko Corporation | Photosensitive resin composition and use of the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000112126A (en) * | 1998-10-01 | 2000-04-21 | Nitto Denko Corp | Negative photoresist composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2242106A1 (en) * | 1972-08-26 | 1974-03-21 | Agfa Gevaert Ag | LIGHT SENSITIVE PHOTOGRAPHIC MATERIAL |
| DE3335309C1 (en) * | 1983-09-29 | 1984-08-16 | Du Pont de Nemours (Deutschland) GmbH, 4000 Düsseldorf | Photographic recording process using light curable materials |
| DE4007236A1 (en) * | 1989-03-20 | 1990-09-27 | Siemens Ag | High resolution positive working photoresists - comprising polymer contg. carboxylic acid anhydride or phenolic hydroxyl gps. and substd. 1,4-di:hydro:pyridine cpd. as photoactive agent |
| DE69222203T2 (en) * | 1991-03-05 | 1998-01-15 | Nitto Denko Corp | Heat-resistant, positive-working photoresist composition, photosensitive substrate, and process for producing a heat-resistant positive pattern |
-
1992
- 1992-10-26 JP JP04287384A patent/JP3093055B2/en not_active Expired - Lifetime
-
1993
- 1993-07-05 EP EP19930110730 patent/EP0578177B1/en not_active Expired - Lifetime
- 1993-07-05 DE DE1993608403 patent/DE69308403T2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5521034A (en) * | 1993-05-07 | 1996-05-28 | Nitto Denko Corporation | Individual identification label |
| JPH07271034A (en) * | 1994-03-29 | 1995-10-20 | Nitto Denko Corp | Heat-resistant negative photoresist composition, photosensitive substrate and negative pattern forming method |
| WO1998004959A1 (en) * | 1996-07-29 | 1998-02-05 | Nitto Denko Corporation | Negative photoresist compositions and use thereof |
| US6048663A (en) * | 1996-07-29 | 2000-04-11 | Nitto Denko Corporation | Negative-working photoresist compositions and and use thereof |
| US6746816B2 (en) | 2000-11-08 | 2004-06-08 | Nitto Denko Corporation | Photosensitive resin composition and circuit board |
| US7008752B2 (en) | 2004-03-17 | 2006-03-07 | Nitto Denko Corporation | Photosensitive resin composition and use of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69308403D1 (en) | 1997-04-10 |
| JP3093055B2 (en) | 2000-10-03 |
| EP0578177B1 (en) | 1997-03-05 |
| DE69308403T2 (en) | 1997-06-12 |
| EP0578177A3 (en) | 1994-08-03 |
| EP0578177A2 (en) | 1994-01-12 |
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